We report, for the first time, a detailed study at river water and hyporheic zone systems through collection and analyses of shallow sediments and selected source rocks, pore water, and river water from forty-two locations at the Chianan Plain (CP), SW Taiwan. The study was focused to understand the possible changes in the river water and sediment chemistry as a consequence of high arsenic (mean +/- SD = 71.28 +/- 16.24 mu g/L, n=46) groundwater discharge to three major rivers in the plain. The study shows, except few locations, As concentration in river sediments corresponds to average As concentration in soil and upper crustal abundance and of source rock. Sequential extraction indicates that As is mostly bound to FeOOH. No enrichment of arsenic in river sediments or depletion of aqueous As and iron in pore water was observed down to the maximum sampling depth of 1.7 m although manganese is enriched in sediments. Dissolved As concentrations in the river sediments are much lower compared to the hotspots in the CP aquifers. This suggests that no As attenuation processes are active or they cannot be detected in this zone. Mn precipitates at higher redox level compared to Fe and As and thus attenuates in the studied zone. (C) 2017 Elsevier B.V. All rights reserved.